Parameterization and quantification of two key operando physio-chemical descriptors for water-assisted electro-catalytic organic oxidation
Abstract Electro-selective-oxidation using water as a green oxygen source demonstrates promising potential towards efficient and sustainable chemical upgrading. However, surface micro-kinetics regarding co-adsorption and reaction between organic and oxygen intermediates remain unclear. Here we syste...
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Nature Portfolio
2024-11-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-54318-7 |
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| author | Bailin Tian Fangyuan Wang Pan Ran Luhan Dai Yang Lv Yuxia Sun Zhangyan Mu Yamei Sun Lingyu Tang William A. Goddard Mengning Ding |
| author_facet | Bailin Tian Fangyuan Wang Pan Ran Luhan Dai Yang Lv Yuxia Sun Zhangyan Mu Yamei Sun Lingyu Tang William A. Goddard Mengning Ding |
| author_sort | Bailin Tian |
| collection | DOAJ |
| description | Abstract Electro-selective-oxidation using water as a green oxygen source demonstrates promising potential towards efficient and sustainable chemical upgrading. However, surface micro-kinetics regarding co-adsorption and reaction between organic and oxygen intermediates remain unclear. Here we systematically study the electro-oxidation of aldehydes, alcohols, and amines on Co/Ni-oxyhydroxides with multiple characterizations. Utilizing Fourier transformed alternating current voltammetry (FTacV) measurements, we show the identification and quantification of two key operando parameters (ΔI harmonics/I OER and ΔV harmonics) that can be fundamentally linked to the altered surface coverage ( $$\Delta {\theta }_{{{{{\rm{OH}}}}}^{*}}/{\theta }_{{{{{\rm{OH}}}}}^{*}}^{{{{\rm{OER}}}}}$$ Δ θ OH * / θ OH * OER ) and the changes in adsorption energy of vital oxygenated intermediates ( $${\Delta G}_{{{{\rm{OH}}}}*}^{{{{\rm{EOOR}}}}}-{\Delta G}_{{{{\rm{OH}}}}*}^{{{{\rm{OER}}}}}$$ Δ G OH * EOOR − Δ G OH * OER ), under the influence of organic adsorption/oxidation. Mechanistic analysis based on these descriptors reveals distinct optimal oxyhydroxide surface states for each organics, and elucidates the critical catalyst design principles: balancing organic and M3+δ−OH* coverages and fine-tuning ΔG for key elementary steps, e.g., via precise modulation of chemical compositions, crystallinity, defects, electronic structures, and/or surface bimolecular interactions. |
| format | Article |
| id | doaj-art-b2df623776ab4108964b454b2a749ddd |
| institution | OA Journals |
| issn | 2041-1723 |
| language | English |
| publishDate | 2024-11-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-b2df623776ab4108964b454b2a749ddd2025-08-20T02:22:16ZengNature PortfolioNature Communications2041-17232024-11-0115111410.1038/s41467-024-54318-7Parameterization and quantification of two key operando physio-chemical descriptors for water-assisted electro-catalytic organic oxidationBailin Tian0Fangyuan Wang1Pan Ran2Luhan Dai3Yang Lv4Yuxia Sun5Zhangyan Mu6Yamei Sun7Lingyu Tang8William A. Goddard9Mengning Ding10Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing UniversityKey Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing UniversityKey Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing UniversityKey Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing UniversityKey Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing UniversityKey Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing UniversityKey Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing UniversityKey Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing UniversityKey Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing UniversityMaterials and Process Simulation Center (MSC) and Liquid Sunlight Alliance (LiSA), California Institute of TechnologyKey Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing UniversityAbstract Electro-selective-oxidation using water as a green oxygen source demonstrates promising potential towards efficient and sustainable chemical upgrading. However, surface micro-kinetics regarding co-adsorption and reaction between organic and oxygen intermediates remain unclear. Here we systematically study the electro-oxidation of aldehydes, alcohols, and amines on Co/Ni-oxyhydroxides with multiple characterizations. Utilizing Fourier transformed alternating current voltammetry (FTacV) measurements, we show the identification and quantification of two key operando parameters (ΔI harmonics/I OER and ΔV harmonics) that can be fundamentally linked to the altered surface coverage ( $$\Delta {\theta }_{{{{{\rm{OH}}}}}^{*}}/{\theta }_{{{{{\rm{OH}}}}}^{*}}^{{{{\rm{OER}}}}}$$ Δ θ OH * / θ OH * OER ) and the changes in adsorption energy of vital oxygenated intermediates ( $${\Delta G}_{{{{\rm{OH}}}}*}^{{{{\rm{EOOR}}}}}-{\Delta G}_{{{{\rm{OH}}}}*}^{{{{\rm{OER}}}}}$$ Δ G OH * EOOR − Δ G OH * OER ), under the influence of organic adsorption/oxidation. Mechanistic analysis based on these descriptors reveals distinct optimal oxyhydroxide surface states for each organics, and elucidates the critical catalyst design principles: balancing organic and M3+δ−OH* coverages and fine-tuning ΔG for key elementary steps, e.g., via precise modulation of chemical compositions, crystallinity, defects, electronic structures, and/or surface bimolecular interactions.https://doi.org/10.1038/s41467-024-54318-7 |
| spellingShingle | Bailin Tian Fangyuan Wang Pan Ran Luhan Dai Yang Lv Yuxia Sun Zhangyan Mu Yamei Sun Lingyu Tang William A. Goddard Mengning Ding Parameterization and quantification of two key operando physio-chemical descriptors for water-assisted electro-catalytic organic oxidation Nature Communications |
| title | Parameterization and quantification of two key operando physio-chemical descriptors for water-assisted electro-catalytic organic oxidation |
| title_full | Parameterization and quantification of two key operando physio-chemical descriptors for water-assisted electro-catalytic organic oxidation |
| title_fullStr | Parameterization and quantification of two key operando physio-chemical descriptors for water-assisted electro-catalytic organic oxidation |
| title_full_unstemmed | Parameterization and quantification of two key operando physio-chemical descriptors for water-assisted electro-catalytic organic oxidation |
| title_short | Parameterization and quantification of two key operando physio-chemical descriptors for water-assisted electro-catalytic organic oxidation |
| title_sort | parameterization and quantification of two key operando physio chemical descriptors for water assisted electro catalytic organic oxidation |
| url | https://doi.org/10.1038/s41467-024-54318-7 |
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